Disazo dyestuffs



Patented Sept. 1, 1953 DISAZO DYESTUFFS Hans Ischer, Basel, Switzerland, assignor to- Sandoz A. G., Basel, Switzerland, a Swiss No Drawing. Application July 5, 1951, Serial No.

235,363; In Switzerland July 6,1950

l The present invention relates to valuabledisazo dyestuffs of the type of wherein R stands for the radical of a hydroxybenzoic acid and R stands for'the radical of an N-acyl derivative of an amino-hydroxy-na'ph- 'thalene sulfonic acid.

An object of the present invention is the embodiment of a new group of disazo dyestuffs of the said type, which are characterized by superior properties as com-pared with known dyestuffs of the said type. Since the said known dyestuffs leave something to be desired from the standpoint of capacity to draw onto textile fibers, such as cotton and regenerated cellulose, itis a primary object of the invention to provide a new group of such dyestuffs which are distinguished by their outstanding capacity to draw'onto the aforesaid textile fibers. This superiority is of manifest practical significance, since a poorly drawing dyestufi is correspondingly uneconomical to use.

The foregoing and other objects are realized according to the present invention by the new group ofdyestufis of the following constitution:

(iJHa wherein R stands for the radical of l-liyd'r'oxybenzene-Z-carboxylic acid, l-hydroxy-fi-rnethylbenzene-Z-carboxylic acid, l-hydroxyef -meth oxy-benzene 2 carboxylic acid, l-hydrox-y-fimethyl-benzene-Z-carboxylic acid, l-hydroxy-G- chlorobenzene-2-carboxylic acid, l-hydroxy-G- su1fo-benzene-2-carboxy1ic acid or l-hydroxy-fi methy1-benzene-2-carboxylic acid and R stands for the radical of an N-acyl derivative of -1-amino-5-hydroxynaphthalene 7 sulfonic' acid, 1- amino-8-hydroxynaphthalene-4-sulfonic acid, 1- amino-S-hydroxy naphthalene-6-sulfonic acid, 1-amino-8-hydroxynaphthalene 3,6 disulfonic acid, 1 amino-8-hydroxy-naphthalene-4,G-disulfonic acid, 2-amino-5-hydroxynaphtha1ene-7- sulfonic acid, 2-amino-G-hydroxy-naphthalene- 8-sulfonic acid, 2-amino-S-hydroxy-naphthalene-G-sulfonic acid or 2-amino-5-hydroxynaphthalene-l,7-disu1fonic acid. These new dyestuffs are unexpectedly characterized by outstanding capacity for drawing onto cotton and regenerated cellulose fibers as well as by other superior properties hereinafter'enumerated.

6 Claims. (01.2,60-187) The aforesaid new disazo dyestuffs of the present invention are conveniently prepared by coupling the diazo compound of the aminoazo dyehstuff oftheformula wherein R stands for the radical of 1-hydroxybenzene-Z-carboxylic acid, 1-hydroxy-5-methylbenzene2-carboxylic acid, l-hydroxy-S-methoxy-benzene 2 carboxylic acid, 1-hydroxy-6- methyl-benzene-2-carboxylic acid, 1-hydroxy-6- chlorobenzene-2-carboxylic acid, l-hydroxy-G- sulfobenzene-2-carboxy1ic acid or l-hydroxy-3- methyl-benzene-2-carboxylic acid, with 'an N- acyl derivative 'of an amino-hydroxy-naphthalene-sulfonic acid such as:

1 amino-5-hydroxy naphthalene '7 sulfonic acid,

" ,1 amino-B-hydroxy a naphthalene 4 sulfonic acid, 1 amino 8 hydroxy naphthalene-G-sulfonic acid,

' i 'amino-8-l ydroiiy naphthalene-3,6-disulfonic acid,"

l-amino-8-hydroizy naphthalene-4,6-disulfonic acid, Z-amino 5 hydroxy-naphthalene 7 sulfonic 2 amino-6-hydroxy naphthalene 8 sulfonic acid,

Z-amino-8-hydroxy-naphthalene-6-sulfonic acid "or- -2-amino-'-5-hydroxy naphthalene-1,7-disu1fonic acid.

The aminoazo dyestuffs employed, as afore- ,said as starting products can be prepared for example by coupling diazotized 1-amino-4-nitro benzene with l hydroxybenzene-Z-carboxylic acid or a derivative thereof which couples in para position to'- the OH-group, reducing the nitro group in the resultant product with sodium sulfide, condensing the thus-obtained aminoazo dyestuff with 3-methyl-4-nitrobenzoyl chloride,

and finally also reducing the thus-introduced arr-a'cyl derivative of one of the hereinbeforeenumerated amino-hydroxv-naphthalene sulfonic acids is preferably effected in alkaline medrum.

The new dyestufis thus prepared dye cotton and regenerated cellulose in scarlet-red to bluered shades which, upon aftertreatment with copper salts, become fast to washing and to light. In so far as any of the new dyestuffs contains an external free amino group, it can be further diazotized on the fiber and coupled with 2-hydroxy-naphthalene, producing red dyeings of very good fastness to washing and capable of being discharged to pure white.

The following examples set forth representative exemplary embodiments of the invention, and these examples are intended to be solely illustrative and not at all limitative. In these examples, the parts are by weight and the temperatures are expressed in degrees centigrade. The term soda" refers to sodium carbonate.

Example 1 39 parts of the aminoazo dyestuff of the formula COOH CH;

are dissolved in 500 parts of water and parts of concentrated aqueous caustic soda solution. To the resultant solution, there are then added successively, at 10, 7 parts of sodium nitrite and 40 parts of concentrated sulfuric acid. The thus-obtained suspension is stirred for 1 to 2 hours at 10 until the diazotization is completed. The diazo compound is then run into a solution of 39 parts of 2-carbethoxyamino-5-hydroxynaphthalene-l,7-disulfonic acid and 50 parts of calcined soda in 400 parts of water. Coupling takes place very rapidly and, after stirring for CODE Example 3 39 parts of the aminoazo dyestufi of the formula COOH ECO-IGN-ONHCOO-NH:

are dissolved in 500 parts of water and 10 parts of concentrated aqueous caustic soda solution. To the thus-obtained solution, there are then successively added 7 parts of sodium nitrite and 40 parts 01' concentrated hydrochloric acid at 10. The resultant suspension is stirred for 1 to 2 hours at 10 until the diazotization is complete. The diazo compound is then run into a solution of 34.3 parts of Z-benzoylamino-S-hydroxy-naphthalene-7-sulfonic acid and parts of calcined soda in 400 parts of water. Coupling takes place very rapidly and, after stirring for 2 hours, the precipitated dyestuif is filtered oflf and dried at 90 under reduced pressure.

The new dyestufi, a red-brown powder, dissolves in water with red coloration and dyes cotton and regenerated cellulose in scarlet-red shades which become very fast to washing and to light upon being aftercoppered. The dyestuff corresponds to the following formula:

OH: OH

2 hours, the precipitated dyestuff is filtered off and dried at 90 under reduced pressure.

The new dyestuff, a red-brown powder, dissolves in water with red coloration and dyes cotton and regenerated cellulose in scarlet-red shades which are rendered fast to washing and to light by aftercoppering.

Example 40.5 parts of the aminoazo dyestufl. of the formula COOH $13: HOGM NHCO NH.

are dissolved in 500 parts of water and 10 parts of concentrated aqueous caustic soda solution. 7 parts of sodium nitrite and 40 parts of concentrated hydrochloric acid are then successively added at 10. The reaction mixture is stirred until, after about 2 hours, the diazotization is complete, whereupon it is combined with a solution of 35.8 parts of 2-(4'-aminobenzoyl)- amino 8 hydroxynaphthalene-fi-sulfonic acid and 50 parts of calcined soda in 00 parts 01 Example 4 39 parts or the aminoazo dyestufi of the formula COOH OH:

are dissolved in 500 parts of water and 10 parts of concentrated aqueous caustic soda solution. 7 parts of sodium nitrite and 40 parts of concentrated hydrochloric acid are then added successively at 10. The resultant suspension is stirred for l to 2 hours at 10 until the diazotization is complete. The diazo compound is then run into a solution of 33.9 parts of 2-carbethoxyamino5-hydroxy naphthalene-'l-sulfonic acid and 50 parts of calcined soda in 400 parts of water. Coupling takes place very rapidly and, after stirring for 2 hours, the precipitated dyestuff is filtered off and dried at under reduced pressure.

The new dyestufi, a red-brown powder, dissolves in water with red coloration and dyes cotton and regenerated cellulose in scarlet-red shades which become very fast to washing and s 6 light upon being aftercoppered. The dyestuff cessively at The resultant suspension is corresponds to the following formula: stirred for 1 to 2 hours at 10 until the diazotiza- 000E (3H3 on BOaH- NHCOOC2H5 Example 5 tion is complete. The diazo compound is then 10 run into a solution of 37.2 parts of 2-(3-methyl- 39 parts of the aminoazo dyestufi of the 4' aminobenzoyl) amino 5 hydroxy naphformula thalene-I-sulfonic acid and 50 parts of calcined OOOH CH3 soda in 400 parts of Water. Coupling takes place I I very rapidly and, after stirring for 2 hours, the

G C precipitated dyestuff is filtered off and dried at 90 under reduced pressure.

are dissolved in 500 parts of water and 10 parts The new dyestuff, a red-brown powder, disof concentrated aqueous caustic soda solution. solves in water with red coloration and dyes To the resultant solution, there are then succotton and regenerated cellulose in scarlet-red cessively added, at 10, 7 parts of sodium nitrite shades which become very fas to Washing and to and parts of concentrated hydrochloric acid. light upon being aftercoppered. The dyestuff The resultant suspension is stirred for 1 to 2 corresponds to the formula: 1

COOH om OH 0 This dyestuff can be further diazotized on the fiber and coupled with Z-hydroxy-naphthalene, whereupon bluish-red dyeings are obtained which are fast to washing and can be discharged to pure whiteness.

hours at 10 until the diazotization is complete. 3 The diazo compound is then run into a solution of 35.8 parts of 2-(4-aminobenzoyl)-amino-5- hydroxy-naphthalene-7-sulfonic acid and parts of calcined soda in 400 parts of water.

Coupling takes place very rapidly and, after stir- 35 Example 7 ring for 2 hours, the precipitated dyestufi is 39 parts of the aminoazo dyestufi of the forfiltered off and dried at 90 under reduced presmula:

sure. COOK OH:

The new dyestuff, a red-brown powder, dis- 40 I I solves in water with red coloration and dyes -N=N-C N1-Io0-Nm cotton and regenerated cellulose in scarlet-red shades which become very fast to washing and are dissolved in 500 parts of water and 10 parts to light upon being aftercoppered. The dyestuff of concentrated aqueous caustic soda solution. corresponds to the formula: '7 parts of sodium nitrite and 40 parts of concen- SOaH -NrrooONH,

This dyestuff can be further diazotized on the trated hydrochloric acid are then added succesfiber and coupled with 2-hydroxy-naphthalene, sively at 10. The resultant suspension is whereupon bluish-red dyeings are obtained which stirred for 1 to 2 hours at 10 until the diazotizaare fast to washing and which can be discharged tion is complete. The diazo compound is then to pure whiteness. run into a solution of 42.3 parts of 2-benzoyl- Example 6 amino 5 hydroxy naphthalene-1,7-disulfonic acid and 50 parts of calcined soda in 400 parts of 39 part f t aminoazo dy tufi f t water. Coupling takes place very rapidly and,

formula: after stirring for 2 hours, the precipitated dye- 00 OH CH3 stuff is filtered off and dried at under reduced I pressure.

I O NHco-NH, The new dyestufi, a red-brown powder, dissolves in water with red coloration and dyes cotare dissolved in 500 parts of water and 10 parts 5 ton and regenerated cellulose in scarlet-red of concentrated aqueous caustic soda solution. shades which, upon aftercoppering, became very '7 parts of sodium nitrite and 40 parts of confast to washing and to light. The dyestufi corcentrated hydrochloric acid are then added sucresponds to the formula:

COOH CH: (I)H V 7 son: NHC o-Q By replacing the diazo component and the couample be replaced by the radical of l-hydroxy- Fling 6011111011911? of any Q? the feregqine 5-methyl-benzene-2-carboxylic acid, l-hydroxyamples by equivalent quantities of the di-azo and 5 methoxy benzene z carboxylicacid1 hydmxy cou iin com onents enumerated in the addition al eizampl s set forth in the following table, 5 s'methylbenzene'z'carboxyhc acld, l'hydroxyand otherwise proceeding according to the pre- 6-011101'0-beI1Zene-2-0arb0Xy1i0 ac d, l-hydroxys r p s f the pr c exampl he r 6-su1fo-benzene-2-carboxy1ic acid or l-hydroxyslplfnding dadditigrfindiggig sh gg gfigg ggg' 3-methyl-benzene-2-carb0xylic acid, yielding in ese ro uce s ton is yed therewith, and otherwise have proD- 10 each case dyestufi Wlth snmlar erties similar to those of the precedingly (16- This means. of eeurse, that a pondin ly scribed dyestufis. substituted diazo component is employed.

Diazo Component: Diazo Compound from the Aminoazo Dyestufi- NHC -NH Dyeing on i gP R N 0 Q Coupling Component Cotton wherein R is the radical of 2-benzoyiamino-5-hydroxy-naphthalene-7-su1ionic acid-.- Scarlet. 2-acetyiamino-5-hydroxy-naphthaiene-7-sulfonic acid..... Do. 2 cinnamoylamino 5 hydroxy naphthalene 7 5111- D0.

fonic acid. 2 (2 carboxybenzoyl) amino 5 hydroxy naphtha- Do.

lene-7-suifonic acid. 2 (4 ammobenzoyi) amino 5 hydroxy naphthalene- D0.

7-sulfonic acid. 2 (3 aminobenzoyi) amino 5 hydroxy naphthalene- Do.

7-su1fonic acid. 2 (4 aminobenzoyl) amino 8 hydroxy naphthaienered.

fi-sulfonic acid. 2 (3 aminobenzoyi) amino 5 hydroxy naphthalene, scarlet.

1,7-disulfonic acid. 2-benzoylamino-8-hydroxy-naphtha1ene-6-sulfonic acid.- red. l-benzoy1amino-8-hydroxy-naphthalene-G-suifonic acid... blue-red. 1 (4 aminobcnzoyl) amino 8 hydroxy naphthalene- Do.

fi-suifonic acid. 1 (4' aminobenzoyl) amino 5 -hydroxy naphthalenescarlet.

7-suif0nic acid. 1 (4-aminobenzoyl) -amino-8-hydroxy-naphthalcne-4,6- blue-red.

disulionic acid. 2- (3-methyl-4 -amiuobcnz0y1) -amino-8-hydroxy-naph- Do.

thaiene-fi-sulionic acid. 2- (4 -methyl-3-aminobenzoyl) -amino-5-hydroxy-naphred.

thalene-7-sulf0nic acid. 2-(3-methy1-4-aminobenzoyl)-amino-5-hydroxy-naph- Do.

thaiene-7-suifonic acid. 2-(3-mcthyl-4-aminobcnzoyl)-amino-5-hydroxy-naph- Do.

thaJcne-1,7-disulf0nic acid. 1-(3-methy1-4-aminobenzoyi)-amino-5-hydroxy-naph- Do.

thalene-Wsulionic acid. 2 (4 benzoylaminobenzoyl) -amin0 5 -hydroxy -naph scarlet.

thalene-l,7-disuifonic acid. 1 (4' benzoylaminobenzoyi) amino -8 -hydroxy -naph blue-red.

thalene-4,6-disu1ionic acid. 2-ca bethoxyamino-5-hydroxy-naphtha1ene-7-suiionic scarlet.

acid. 2-beizoylamino -5-hydroxy -naphtha1ene-1,7-disu]1'onic D0.

acl 2-cin1amoy1amino -8 -hydroxy-naphtha1ene fi-sulfonio red.

2-acetylamino-6-hydr0xy-naphtha1ene-8-su1fonic acid... blue-red. 1 (4 -aminobenzoyl) amino -8 -hydroxy -naphthalene-4- Do.

sulfonic acid.

l-be%oyiamino-8-hydroxy-naphthalene-3,6-disu1fonic Do.

aci

1hygroxybenzene-2-carboxylic acid o In the foregoing table, the l-hydroxybenzene- The following are formulae of representative 2-carboxy1ic acid (R) moiety may in each exproducts of the foregoing Examples 8 to 33:

No.9. coon CH3 on 80:11 NHCOCHa 18. No (1003 ?Ha on I| IHCONH:

No.19. 10011 cm on HOG-N -NONHC OON=N 31 SOzH NHC oQ-wm No.29 COOH CH; OH:

No.30. COOH CH:

No.31. COOH OH:

I C H:

I C H:

COOH CH:

Example 34 Dyeing with a representative dyestufi according to the present invention may be carried out for example as follows: v

100 parts of vegetable textile material, for instance cotton, are entered at 20 C. into a neutral bath containing parts of Glaubers salt and 1 For after-treatment with acopper salt the direct dyed material is treated for minutes at a temperature of 60 to 70 C. in a bath containing 2 parts of copper sulfate and 3 parts of acetic acid whereupon the material is washed oil with cold water, squeezed and dried.

The after-coppered dyeing, the shade of which being not very much different from that of the part of the dyestuff c rrespo d to the follow direct dyeing showsvery good fastness to light ing formula v0 0 OH CH! and an excellent fastness to washing.

I OH

BOaH

' Example 35 The dyestufi's accordin to the present invention may also be diazotized and developed on the fiber insofar as the dyestuffs contain a free amino group. The dyeing method may be carried out in the following way:

parts of cotton being direct dyed in the COOH CH3 SOaH- are immersed for 30 minutes in a cold bath containing 2 parts of sodium nitrite and 3 parts of sulfuric acid 66 B. During the diazotizing operation the dyed textile material is to be protected against sun-light. After rinsing for a short time in slightly acidified cold water, the

carboxylic acid and l-hydroxy-3methyl-ben-- zene-2-carboxylic acid and wherein R stands NEG OGNH:

carboxylic acid, 1-hydroxy-5-methoxy-benzene- 2-carboxylic acid, l-hydroxy-6-methyl-benzene- Z-carboxylic acid, l-hydroxy-6-chiorobenzene-2- carboxylic acid, 1 hydroxy-fi-su1fo-benzene-2- for an N-acyl'ated radical of an amino-hydroxynaphthal'ene sulfonic acid selected from the material is entered into a cold development bath group consisting of 1-amino-5-hydroxy-naphcontaining 1 part of 2-hyd'roXynaphthalene and 1 part of sodium hydrate of 40 B. After treatment for to minutes in this bath the material is taken ofi, thoroughly washed with cold Water and dried.

The thus obtained red dyeing is distinguished by an excellent fastness to washing and especially by good dischargeability, both with a neutral and an alkaline discharge paste.

thalene-7-sulfonic acid, l-amino-S-hydroxynaphthalene-4-sulfonic acid, 1 amino-S-hydroxy-naphthalene-G-su1fonic acid, l-amino-8- hydroxy naphthalene 3,6 disulfonic acid, 1-

20 amino 8 hydroxy-naphthalene-4,6-disulfonic acid, 2 amino-5-hydroxy-naphtha1ene-7-sulfonic acid, 2-amino-6-hydroxy-naphthalene-8- sulfonic acid, 2-amino-8-hydroXy-naphthalenefi-sulfonic acid and 2-amino-5-hydroxy-naph- Having thus disclosed the invention, what is 25 thalene-1,7-disulfonic acid.

claimed is:

coon

2. The disazo dyestuff of the formula COOH COOH

COOH

SOaH -NH00 3. The disazo dyestuif of the formula CH3 OH 4. The disazo dyestufi of the formula NHC 0 ONE 5. The disazo dyestuff of the formula CH: on

COOH

1. A disazo dyestufi corresponding to the:

formula 7 wherein R stands for the r'adical of a l-hydroxybenzene-Z-carboxylic acid selected from the group consisting of I-hydroxybenzene-2-carboxylic acid, 1 hydroxy-5-methy1benzene-2- 6. The disazo dyestufi of the formula 0H3 OH HANS ISCHER.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,663,950 Neelmeier et a1. Mar. 27, 1928 2,228,321 Messmer Jan. 14, 1941 2,458,776 Grandjean Jan. .11, 1949 

4. THE DISAZO DYESTUFF OF THE FORMULA 